Computational investigation of the vibrational and electronic states of S2N2

The structures and vibrational frequencies of the ground and excited states of S2N2 have been calculated using density functional (DF) methods. Time-dependent DF theory (TDDFT) has been used to calculate the excitation energies of the lowest 20 singlet-singlet transitions using a variety of methods. All computational methods predict a small highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. There is some disagreement in the ordering of the beg and bag pi orbitals. This is reflected in the ordering of the B-2u and B-3u states from the TDDFT calculations. The excitation energies and oscillator strengths strongly suggest it is the transitions to these states that are responsible for the experimental electronic spectrum. The calculated geometries and vibrational frequencies for these two states show that both have C-2v equilibrium structures. Modelling of the vibrational progressions and band shapes suggest that the ordering of the states is B-2u < B-3u. Bond order calculations indicate significant S-S pi bonding in the ground state and that this is enhanced in the B-2u excited state. The geometry of this state distorts by folding of the planar ring to increase the trans-annular S-S bonding. (C) 2003 Elsevier B.V. All rights reserved.